Gasoline fuel additives



about 10 years because of corrosion.

United States Patent oAsoLnsE FUEL ADDITIVES Charles C. Shepherd,Berkley, Mich assignor to Ethyl Corporation, New York, N. Y., acorporation of Delaware No Drawing. Application May 28, 1953, Serial No.$58,185

13 Claims. (c1. 44-66) This invention relates to a new class oforganicmaterial. More particularly, the present invention relates to anovel class of metallic monobasic acid compounds of particular utilityas corrosion inhibitors and stabilizers.

The need for corrosion inhibitors in petroleum products particularly ingasoline, has long been known. The storage, handling and transferoperations associated with petroleum products, especially of thegasoline boiling range necessitates the use of iron and steelcontainers, pipe lines and the like. If it were possible, or at leasteconomically feasible to maintain such hydrocarbon products in anessentially anhydrous condition, corrosion undoubtedly would be almostnon-existent. However, during the manufacturing, storage and shipmentoperations to which fuel is subjected,-considerable quantities of waterare encountered, particularly on exposure to air, and as a result suchfuel contains substantial quantities of water. Thus, tankers and pipelines are generally highly susceptible to corrosion resulting from thewet gasoline contained therein. This corrosion is especiallydeleterious, often resulting in an extremely short period during whichthe tankers and pipe lines can be utilized. In the case of tankers usedfor transporting gasoline there have been estimates that the effectivelife is somewhat less than In the case of pipe lines, it has been statedthat the carrying capacity may be reduced by more than 12 percent in oneyear if no efiort is made to control corrosion. It has been furtherstated that this effect results from the formation-and growth of rustfilrrls which increase the roughness of the pipe causing increased"friction losses and proportionately increased power costs to maintainthe original capacity.

Gasoline storage tanks are also subject to corrosion Such tanks aresusceptible to corrosion attack of several different types. On the onehand 'there isa tendency to corrode'in the bottoms of the tanks bevcauseof the concentration of water b'ottoms 'at these points. Likewise, thereis a severe tendency for corrosion to occur at the gasoline leveland'also in the vapor phase,

that is, above the surface of the fuel. In thecase of storage tankcorrosion the efiect becomes especially significant in that frequenttank cleaning operations are required. Obviously such operationsaredifficult, costly, and time consuming.

Another type of fuel corrosion results from the storage of-gasoline ingasoline drums which are often made from hot or cold rolled steel, orgalvanized iron. Another 'type of metallic container susceptible tocorrosion is the fuel tank of motor vehicles such as automobiles,trucks, and buses.

In each of the aforementioned types of 'fuel containers the corrosionresults in premature destruction of utility, and, likewise, results intheformation of rust, scale, and other sludge deposits whichcause'discolo'ration of the 2,798,797 Patented July 9, 1957 2 fuel andthe clogging of filters, fuel pumps, carburetors, and the like.

As indicated previously such corrosion generally oc} curs atthe'solid-liquid-liquid interface, that is, the point 5 of contactbetween the metallic container, the hydrocarbon phase and the aqueousphase. Such corrosion re sults from the presence of water in bothtreated and untreated hydrocarbon fuel. That is to say, corrosion is aserious problem Whether or not the fuel contains antiknock agents orother a'djuvants. However, in the case of -fuels containing or-ganolead'antiknock compositions another problem is encountered. It has beenfound that the presence of water in fuel containing organic brominecompounds, generally used as lead scavengers, results in a chemicalreaction producing halogen acids, particularly hydr'obromic acid. Thisresults in a loss of effective scavenging material as well as acontribution to the overall corrosion problem. As an example of thismechanism, it has been proposed that the reaction between the metalsurface, to wit: zinc, iron or both and water and the organic brominecompound results in the formation of a complex mixture of zinc and ironhalides or hydroxides. It is evident, therefore, that such corrosionwill result in a severe etching of the metallic container particularlyat the interface.

It has been proposed heretofore to obviate these corrosion problems bytwo alternative means. First, attempts have been made to apply diversecoatings of plastics, lacquers, metallic phosphates and the like so as30 to protect the metallic interface against the corrosive action.Second, attempts have been made't'o utilize corrosion inhibitors such aschromates and numerous and sundry organic and inorganic substances. It'has been found, however, that neither 'of these methods "has beenentirely satisfactory. In the case of the use of "coating materials forthe metallic containers -the difficulties result from chipping, peelingand etching of the surfaces which result in the formation ofadditionalsolids and the concomitant efiects of sediment formation,discoloration and carburetion 'dificulties. In addition to this, aserious drawback is the expense involved in applying and maintainingsuch coated surfaces. The corrosion inhibitors proposed in the prior artas means for the obviation of this problem have likewise been largelyineifectual since they have not possessed the'proper distributioncharacteristics. In other words,'the inorganic substances tend to behighly' soluble in the aqueous phase and conversely the organicsubstances tend to be highly soluble in the hydrocarbon phase and as aresult there is 'littlejprotection afforded at thesolid-liquid-liquidinterface. This, as indicated hereinbefore, is the point at which themost severe corrosion occurs and consequently the need exists for-aclass of materials which have the proper phase distributioncharacteristics.

It is, therefore, an-objectof the present invention to provide as newcompositions of mature class 'of-compounds of particular effectivenessas corrosion inhibitors and as halogen l'oss prevent-attives. Likewise,it is an ob- :ject of this invention to provide processes forthepre'paration of these new compositions of'matter. Among "theadditional objects of theipresentinvention' is that of pro- 'vidingprocesses for inhibiting'both corrosion and halo'gen' compositions ofmatter a class of partially hydroxylated hydrates of metallic monobasicacid compounds. The materials of the present invention are partiallyhydroxylated polyvalent metallic materials derived from monobasic acidscapable of forming hydrates. Thus, the new compositions of matter of thepresent invention are derived from polyvalent metallic salts of suchacids as fatty acids which can be saturated or unsaturated open chainmonobasic acids or cyclic monobasic acids. Therefore, the partiallyhydroxylated hydrates of metallic monobasic acids can be prepared fromsuch acids a lauric, myristic, palmitic, stearic, arachidic,eicosane-carboxylic, behenic, lignoceric, cerotic, melissic,psyllastearic, naphthenic, oleic, erucic, elaidic, ricinoleic,brassidic, tiglic, citronellic, undecylenic, geranic, linoleic,dehydrogeranic, linolenic and like acids.

As indicated previously the compositions of matter of the presentinvention contain a polyvalent metal. Thus, the materials of the presentinvention can contain such polyvalent metals as magnesium, zinc,thorium, calcium, aluminum, lead, vanadium as vanadyl and the like.

The preferred materials of the present invention are termed partiallyhydroxylated hydrates of metallic monobasic straight chain unsaturatedacids containing from about to 30 carbon atoms per molecule. Likewise,the preferred metallic constituent of the new compositions of matter ofthe present invention is magnesium.

To better understand the nature of the present invention an illustrativematerial, magnesium oleate, is consid' ered in detail.

It has been found that the fatty acid derivatives of metals of thecharacter described hereinbefore are capable of existing in a number ofchemical forms. For example, magnesium oleate can exist in at least fourstates of aggregation as follows:

1. Anhydrous magnesium oleate 2. Magnesium oleate dihydrate 3. Partiallyhydroxylated hydrate of magnesium oleate 4. Basic hydrate of magnesiumoleate The fact that such materials can exist in these diverse states ofaggregation is of extreme importance in their effective utilizationparticularly in the obviation of corrosion as will become still furtherapparent from the discussion hereinafter.

Again referring to the illustrative example, magnesium oleate, thetransformations which occur serve to elucidate, at least in part, thechemical nature of the diverse physical and chemical forms. Anhydrousmagnesium oleate has been shown capable of coordinating or otherwiseincorporating into its molecular structure two molecules of water ofhydration. It has now been found that such hydrated polyvalentderivatives of monobasic acids, for example magnesium oleate dihydrate,can be treated under hydroxylation conditions such that the material istransformed into what is termed a partially hydroxylated hydrate ofmagnesium oleate. The hydroxylation conditions referred to can beproduced in a number of ways. For example, magnesium oleate dihydratecan be subjected to temperatures between about to C. for a period oftime in the order of about six months or more in order to bring about atransformation in the characteristics of chemical structure, physicalappearance, and corrosion effectiveness.

Another variant in producing the hydroxylation conditions for thepreparation of the partially hydroxylated hydrates of metallic monobasicacid compounds of the present invention consists of subjecting apolyvalent metallic compound derived from a monobasic acid totemperatures in the order of about 40 to C., for a period of about threemonths.

In order to further establish the nature of the new compositions ofmatter of the present invention the following simplified explanation ofthe hydroxylation reaction is of help. On subjecting magnesium oleatedihydrate Hydroxylation ii conditions Partially hydroxylated hydrate ofmagnesium oleate As indicated in the above hypothetical reactions theequilibrium as between the magnesium oleate dihydrate represented as Iand the partially hydroxylated hydrate of magnesium oleate, II underhydroxylation conditions favors the formation of the latter. However, itis to be noted that the theoretical end product represented by 111 isapparently not formed in any significant quantity under such conditions.

As indicated hereinbefore the above reactions are believed theoreticallypossible and are presented to explain as nearly as possible the natureof the new compositions of matter of the present invention. However, itis to be understood that such reactions are probably over simplified.For example, it will be noted that the double bonds present in themagnesium oleate dihydrate are susceptible to oxidation when thecompound is treated under the hydroxylation conditions. As a result ofthis, it is probable that at least minute quantities of epoxides,aldehydes, ketones, acids and peroxides are formed during this process.Likewise, it is conceivable that under certain circumstances themolecule may rupture across the double bond to form a number ofindividual chemical entities from what appears to be a simple startingmaterial. Furthermore, in the processes of oxidation and cleavage andunder the conditions of the hydroxylation process the environmentappears favorable for the formation of a number of coordinationcomplexes and the like. In short, it appears that both the nature of thehydroxylation process and the nature of the partially hydroxylatedhydrate of magnesium oleate so formed are of an extremely complexnature, and, therefore, defy more precise definition. The

specific examples presenting experimental data which appear hereinafterwill further indicate the complexity of the processes and products ofthe present invention.

The fact that the hydroxylation of polyvalent metallic salts ofmonobasic acids capable of forming hydrates is of a complex nature isfurther evidenced by considering in somewhat greater detail the natureof the partially hydroxylated hydrates so formed. For example, referringagain to the illustrative material, magnesium oleate, it was found that,in general, the partially hydroxylated hydrate of magnesium oleateexists either as a loosely bonded coordination complex or as a mixtureor agglomeration of diverse components formed during the hydroxylationreaction. As an indication of this fact it has been found that thematerial can be treated with organic solvents such as, for example,ketones, aldehydes and the like with the resulting formation of and/orseparation into two distinct phases. That is to say, on extracting thepartially hydroxylated hydrate of magnesium oleate with acetone it wasfound that a portion of the material re- 75 mained insoluble whereas theremainder of the material synapse was readily soluble. On vaporizing thesolvent subsequent'to the separation, a yellow liquid was obtainedwhereas the insoluble portion remained as a free flowing white powder. Afurther discussion regarding the nature of these materials will bepresented hereinafter.

To further understand the nature of the present invention reference ismade to the following specific examples wherein all parts andpercentages are by weight.

EXAMPLE I Magnesium oleate dihydrate.-To 500 parts of water was added 11parts of magnesium chloride and to 500'p'arts of water was added 15parts of sodium oleate. The resulting homogeneous solutions were mixedin a reaction vessel while stirring. It was found that a whitecrystalline precipitate was formed which, after filtration and airdrying, remained as a free flowing powder. Analysis of'the precipitateso formed disclosed the presence of 3.87 percent of magnesium whereasthe formula requires 3.90 percent of magnesium. Upon subjecting thematerial to X-ray diifractio'n studies a sharp line pattern resultedwith lines at :3.0, 4.10, 6.10, 10.0, 15.95, 18.10, 19.90, 20.35, and21.90 degrees. The magnesium oleate dihydrate prepared as describedabove exhibited a vapor pressure of'8 mm. at 22 C.

EXAMPLE II Anhydrous magnesium oleate;---To 40 parts of the magnesiumoleate dihydrate as prepared in Example I was added 270 parts ofbenzene. The resulting composition was then placed in an all-glassvacuum apparatus and subjected to a'zeo'tropi'c distillation byevaporation under vacuum. In contrast with the crystalline appearance ofthe magnesium oleate dihydrate the anhydrous material wasa tacky yellowglass. 6n subjecting this'rnaterial to magnesium analysis, it was foundthat there was 4112 percent of magnesium present. The formula M'g(C1sII3sO2)z requires 4.14 percent of magnesium. X-ray diffraction studies ofthe material showed a broad diifuse band between 18 and 22.

EXAMPLE III Partially h ydroxylated hydrate 0 magnesium0leate.Approximately 100 parts of magnesium oleate-dihydrate as prepared inExample I was placed in a glass: container in contact with theatmosphere while maintaining the temperature in the order of betweenabout 20 and C. for a period of sixteen months. Under these conditionsit was found that the material had changed from an odorless,free-flowing powder to a waxy material possessing a characteristic odor.

As indicated previously the partially -hydroxylated hydrates formed inaccordance-with the present invention appear to be either loosely bondedcoordination complexes or are aggregates of materials formed during thehydroxylation reaction. A further study of the materials termed hereinas partially 'hydroxylated hydrates was made using the material preparedinExample III. The results of this study are .presented'in Example IV.

EXAMPLE IV Too 500 milliliter Jena funnel was added 30 parts of thematerial prepared in Example III. The material was then extracted withapproximately 100 parts of acetone and the extract separated from theinsoluble residue. The liquid extract was then evaporated resulting inthe formation of 9.9 parts of a yellow liquid amounting to about 33percent of theoriginal material. The acetone insoluble portion amountingto 20.4 parts or 68 percent of 'the starting material remained as afree-fiowing'white powder. .X-ray diffraction patterns showed only abroad diifus'e band from about 20:15 to 22. Both portions of thematerial obtained by the above treatment wefesiib- 6 jected' toanalyses, the results of: which are shown in Represents about 1%perperoxide Olliter). xide Magnesium (percent) Acetone-insolubleresidue:

Magnesium (percent) Eleetrometrie titration (0H as percent Mg(OH) o 0.16 Represents 4% magnesium oleate.

Mg oleate dihydrate 3.87.

From the results of the experiments described in Example IV it isevident that the partially, hydroxylated hydrates represent either acomplex coordination compound or an aggregation of a number of complexreaction products. Likewise, it'isapparent from the data representedsupra that the equilibria of the illustrative hypothetical reactionspresented hereinbefore find support in the experimental work. That is,the compound as partially hydroxylated hydrate of magnesium oleatecontains at most 5.32 percent of magnesium whereas the dihydrate and thetheoretical. end product represented by III re.- quire respectively 3.90and 7.18' percent of magnesium. Similarly, reference to Table Iindicates the presence of about .1 percent of peroxide oxygen which isin conform itwith. the preceding considerations regarding thesusceptibility of the double bonds to undergo a number of complexoxidation reactions when the hydrated polyvalent metallic derivatives ofmonobasic unsaturated acids are, subjected to hydroxylation conditions.

The. hydroxylation reaction described above with reference to thedihydrate of magnesium oleate occurs with other polyvalent metallicmaterialsderived from mono basic acids. capable of forming hydrates, aswell as with otherrnagnesium containing monobasic acid compounds. Forexample, upon subjecting the hydrate of zinc ricinoleate tohydroxylationconditions, that is, upon subjecting this material to a temperature ofbetween about 20 and about 30 C. fora period of about six months orlonger the transformation herein defined as partial hydroxylationoccurs. That is to say, the material apparentlyundergoes a complexpartial hydroxylation reaction whereby the resulting-material containsasubstantially greater percentage of. .zinc than the startingmaterial,.yetdoes not contain the theoretical amount requiredby the endproductwhich. can be represented by the formula Similarly, bysubjectingthe"hydratesfofaluminum-linoleateandcalcium undecylenate totemperatures between about 20 C. and 50 C. for extended periods of timeof partial hydroxylation reaction occurs with the concomitant effectsindicated above.. Furthermore, upon treating the partially hydroxylate'dhydrates of zinc ricinoleate, aluminum linoleate andcalciumundecylenate-witha solvent such as acetone partition products areobtained. That is to. say, ineac'hof the aforementioned cases. treatmentwith acetone'yields a liquid phase possessing acidic properties whichcontains only minor proportions of the metals zinc, aluminum andca'lciumrespectively. The insoluble products remaining after the acetonetreatment, on the other hand, are free-flowing substances having acharacteristic crystalline appearance. Similar considerations apply tothe other materials within thecontemplation of the present invention.

It has been indicated previously that the existence of the differentforms of the polyvalent metallic salts of monobasic acids is ofconsiderable importance in both corrosion and halogen loss prevention.Likewise, this is undoubtedly due to the solubility and phasedistribution characteristics of these differing forms. For example, ithas been found that, in general, the anhydrous materials, that is, thepolyvalent metallic salts of monobasic acids are extremely soluble inhydrocarbons such as gasoline and the like. Likewise, the hydrates ofsuch materials possess the characteristics of being readily soluble insuch hydrocarbon material, although in general, the coordination orincorporation of the Water of hydration tends to decrease the solubilityto some extent. In contrast with this, it has been found that thepartially hydroxylated hydrates derived from the hydrated material bysubjecting the same to hydroxylation conditions results in a materialwhich has a rather low solubility in hydrocarbon fuel. This discovery isparticularly intercst ing in view of the fact that when this looselybonded coordination complex or aggregation of individual chemicalentities is treated with a material such as, for example, acetone asdescribed hereinbefore one portion of the material so obtained appearsreadily soluble in fuel whereas the residue is practically insoluble.The generalities just presented regarding the solubility of thediffering physical and chemical forms of the polyvalent metallicderivatives of monobasic acids likewise applies in the case of fuel incontact with considerable quantities of water. That is to say, theanhydrous, hydrate and partially bydroxylated hydrate of thesepolyvalent metallic salts possess respectively high, medium and lowsolubility in the fuel. Inasmuch as all of these materials are generallyonly sparingly soluble in water it' is manifest that the partiallyhydroxylated hydrates therefore tend to collect at the liquid-liquidinterface and for this reason are particularly applicable as corrosioninhibitors- By the same token the insoluble residue obtained by theextraction of the partially hydroxylated hydrates possesses the properphase distribution characteristics such that it too is an effectivematerial for this purpose. To more clearly illustrate the precedingdiscussion a large number of experiments were run on both the solubilitycharacteristics of the several forms of the polyvalent metallicmonobasic acid derivatives and the effect of each upon corrosion andhalogen loss prevention.

In order to study the distribution of the illustrative material,magnesium oleate, at low concentration levels in gasoline-water systems,storage tests were carried out in which the samples were stored eitherin two-liter glass stoppered bottles or in two-litered cans of coldrolled steel made with welded seams. The samples consisted of 1,000milliliters of a commercially available hydrocarbon fuel with 100milliliters of water and the desired amounts of the diverse chemicalforms of magnesium oleate. The samples were stored at room temperatureand at convenient intervals milliliter samples of the gasoline phasewere removed and subjected to spectographic analyses. The results of thebottle storage tests are presented in Table II and those of the steelcan tests are shown in GASOLINE AND WATER (GLASS) [Magnesiumconcentrations are shown as lbs. Mg oleate/1000 bbl.]

Table III DISTRIBUTION OF NIAGNESIULM OLEATE BETWEEN GASOLINE AND WATER(STEEL) [ldagncsium concentrations are shown as lbs. Mg oleate i000bbl.]

1 This sample was shaken daily throughout the test period whereas theother samples were not.

In order to determine the effectiveness of the different forms ofmagnesium oleate as a corrosion inhibitor recourse was made to thefollowing type of storage tests. A large number of samples was preparedby blending different quantities of the different forms of magnesiumoleate with commercially available fuels of diverse compositions. Insome instances these fuels had been previously treated withtetraethyllead as an antiknock fluid comprising either tetraethyllead,0.5 theory of bromine as ethylene dibrornide and 1.0 theory of chlorineas ethylene dichloride, or tetraethyllead, and 1.0 theory of bromine asethylene dibromide such that the fuel contained respectively 3.0 or 4.6milliliters of tetraethyllead per gallon. Upon agitating the treated oruntreated fuels with the magnesium oleates, in each instance ahomogeneous fuel blendwas obtained which was then stored in half filledglass bottles each containing 5 or 10 percent of water by volume and aweighed strip of cold rolled steel, the dimensions of which were 1.6 x20 cm. Control tests to establish base lines were run with both leadedand unleaded fuel which did not contain any magnesium oleate derivative.The samples so prepared were stored for a period of two months at 110 F.and at the completion of this period the steep strips were cleaned andreweighed to determine the loss of corroded materials. Likewise,representative samples of fuel were analyzed for total bromine contentto determine the amount of halogen loss. The results of these tests areshown in Table IV. For convenience the different forms of magnesiumoleate are represented in this table as follows: magnesium oleatedihydrate, II, and partially hydroxylated hydrate of magnesium oleateIII.

Table IV SIMULATED BULK STORAGE TESTS [Storage conditions: 2 mo. at 110F., outage, 10 vol. percent water,

steel strips (1.6 x 20 cm.).]

Corrosion Inhibitor TEL Corrosion Br loss, Test No. mL/gal. loss, mg.percent Kind lb./l,000

bbl.

3 III 14 3 III 14 Mg oleate in sample Mg content of gasoline DescriptionCohen. 1 wk. 3 wk. 7 wk. 18 wk.

Anhydrous 24 12.2 2. 9 2. 5 0. 5 Dihydrate 28 0. 4 1. 8 l. 3 0.8Partially Hydroxylated Hydrate 31 1. 2 0 6 0. 5 0.7

The data shown in Table IV indicate that, in general, the hydrates ofpolyvalent metallic salts of monobasic acid compounds are moderatelyeffective as corrosion inhibitors for both treated and untreated fuels,that is, leaded or unleaded fuels. It will be noted, however, that thepartially hydroxylated hydrates of polyvalent metallic monobasic acidsare especially effective in this regard.

A closer study of the partially hydroxylated hydrate of magnesium oleatewas conducted to determine its efiectiveness on corrosion. In additionboth the acetone extract and insoluble residue obtained from thismaterial were tested for this activity. The tests utilized wereessentially identical with those described in accordance with the datapresented in Table IV with the exception that the period of storage wasone month at 110 F. The effectiveness of a number of closer relatedmaterials was likewise determined for comparative purposes. The data ofthese tests are shown in Table V.

Table V SIMULATED BULK sronnon 'rns'rs Storage conditions: 1 mo. at 110F., 50% outage, vol. percent water, steel strips (1.6 x 20 cm.).]

The results of the test Nos. 15, 16, and 17 shown in Table V areparticularly interesting. It can be seen that the partially hydroxylatedhydrate of magnesium oleate completely eliminated corrosion loss andthat the insoluble residue obtained by extracting such material withacetone was also extremely effective. In contrast, however, the acetonesoluble extract of the partially hydroxylated magnesium oleate, althoughutilizable as a corrosion inhibitor, was not as eifective as the othermaterials. Thus, it would appear that the loosely bonded coordinationcomplex or aggregation of chemical entities termed herein as thepartially hydroxylated hydrate of magnesium oleate possesses synergisticcorrosion inhibition qualities. That is to say, the eflfectiveness ofthe acetone extract and the acetone residue would indicate that the sumtotal of these materials would be an effective corrosion inhibitor, butwould not appear to indicate that the partially hydroxylated hydratewould possess the extreme potency as indicated in test No. 15.

From the foregoing it is evident that beneficial effects with regard toboth corrosion prevention and halogen loss prevention can be obtained byblending with hydrocarbon fuels especially those containing or likely tocontain water, hydrates of polyvalent metallic monobasic acid compounds,partially hydroxylated hydrates derived from such compounds bysubjecting them to hydroxylation conditions and the materials obtainedfrom the latter by treatment with an organic solvent such as analdehyde, a ketone and the like. However, because of their greatereffectiveness the partially hydroxylated hydrates and the insolubleresidue obtained therefrom by extraction with such solvents arepreferred.

Although the major portion of the discussion heretofore has beenconcerned primarily with the several physical and chemical forms ofmagnesium oleate it is again to be indicated that this invention isapplicable to the corresponding materials derived from polyvalentmetallic materials derived from monobasic acids capable of forminghydrates. Thus, similar efiects on both corrosion and halogen loss canbe obtained by blending with hydrocarbon fuels the hydrates, partiallyhydroxylated hydrates and solvent extracts and residues of suchmaterials as magnesium elaidate, magnesium ricinoleate, magnesiumstearate, magnesium laurate, magnesium isooleate, magnesium palmitate,magnesium linoleate, zinc naphthenate, thorium naphthenate, leadnaphthenate, vanadyl naphthenate, aluminum oleate, lead oleate, vanadyloleate, aluminum stearate, aluminum ricinoleate,

1O 1 aluminum elaidate, aluminum nervonate, aluminum undecylenate, leadmargarate, aluminum elaeastearate; lead erucate, vanadyl elaeomargarate,zinc palmitate, vanadyl capronate, thorium laurate, thorium capronate,thorium caprylate, and the like.

In accordance with the present invention fuels are improved by addingfrom about one to about fifty pounds per thousand barrels of a hydratedpolyvalent monobasic acid derivative, that is, a member selected fromthe class consisting of hydrates of polyvalent metallic salts ofmonobasic acids, partially hydroxyla'ted hydrates of polyvalent metallicmonobasic acids, organic solvent extracts of partially hydroxylatedhydrates of polyvalent metallic mom obasic a'cid materials and organicsolvent residues of polyvalent metallic monobasic acid materials. Asindicated previously, it is preferred to utilize partially, hy-'droxylated hydrates of polyvalent metallic monobasic acids and organicsolvent residues of partially hydroxylated hydrates of polyvalent'metallic monobasic acid ma terials as corrosion inhibitors and halogenloss preventa tives'. Variations in such employment include introducingthe requisite quantity of such materials into storage tanks, drums, andthe like prior to theintroduction of fuel for storage. Similarly,such'material can be added directly to the fuel, preferably subsequentto conventional refinery operations such as blending. Thus, in general,the materials utilizedas corrosion inhibitors and halogenloss'preventatives in accordance with the present invention can beplaced in contact with fuel at any time prior to or during storage orshipment of the fuel.

As indicated from the experimental data presented hereinbefore corrosionand halogen loss are problems attendant with the storage, shipment andusage of both leaded and unleaded fuel. It has thus been demonstratedthat the materials used in accordance with the present invention ascorrosion and halogen loss preventatives can be utilized with bothleaded and unleaded hydrocarbon fuels. Therefore, the stabilizers of thepresent invention can be successfully utilized in combination withorganolead antiknock agents and organolead-containing compositions suchas antiknock fluids containing diverse halogen scavengers. Similarly,beneficial results are to be obtained by employing such stabilizers incombination with fuels containing other heavy metal derivativesfrequently used as antiknock agents such as iron carbonyl, and the like.Moreover, particular benefits are to be derived by incorporating in theprotected compositions of the present invention conventional amounts oforganic dyes, antioxidants and, indeed, other fuel adjuvants employedfor the obviation of other secondary problems.

Having described the nature of the present invention, the need therefor,and a number of embodiments which can be utilized to eifect especiallybeneficial results, it is not intended that the present invention belimited except within the spirit and scope of the appended claims.

Iclaim:

1. As a new composition of matter, a partially hydroxylated hydrate of ametallic monobasic acid compound prepared by subjecting a hydratedmonobasic acid salt of a polyvalent metal selected from the groupconsisting of magnesium, zinc, thorium, calcium, aluminum, lead andvanadium, said acid being a monobasic straight chain unsaturated acidcontaining from about 10 to 30 carbon atoms per molecule, to atemperature between about 25 and about 50 C. for a period sufficient tobring about a change in chemical composition of said salt, said changebeing an increase in the Weight percent of said metal in said compoundover the weight percent of said metal in said salt, said increase beinginsufiicient to satisfy the weigh-t percentage of said metaltheoretically required by the corresponding basic metal salt.

2. As a new composition of matter, a partially hydroxylated hydrate of amagnesium monobasic acid compound prepared by subjecting a hydratedmonobasic straight chain unsaturated acid salt of magnesium, said acidcontaining from about 10 to about 30 carbon atoms per molecule, to atemperature between about 25 and 50 C. for a period sufficient to bringabout a change in chemical composition of said salt, said change beingan increase in the weight percent of magnesium in said compound over theweight percent of magnesium in salt, said increase being insufficient tosatisfy the weight percentage of magnesium theoretically required by thecorresponding basic magnesium salt.

3. As a new composition of matter, the acetone extract of thecomposition of claim 2.

4. As a new composition of matter, the residue remaining afterextraction with acetone of the composition of claim 2.

5. As a new composition of matter, a partially bydroxylated hydrate ofmagnesium oleate prepared by subjecting a magnesium oleate dihydrate toa temperature between about 25 and about 50 C. for a period sufficientto bring about a change in chemical composition of said dihydrate, saidchange being an increase in the weight percent of magnesium in saidpartially hydroxylated hydrate over the Weight percent of magnesium insaid dihydrate, said increase being insufficient to satisfy the Weightpercentage of magnesium theoretically required by the basic hydrate ofmagnesium oleate.

6. As a new composition of matter, the acetone extract of thecomposition of claim 5.

7. As a new composition of matter, the residue remaining afterextraction with acetone of the composition of claim 5.

8. Gasoline normally in contact with water containing, in amountsufiicient to inhibit corrosion, the composition of Claim 1.

9. Gasoline normally in contact with water containing, in amountsufficient to inhibit corrosion, the composition of claim 2.

10. Leaded gasoline normally in contact with water containing, in amountsufiicient to inhibit corrosion and bromine loss, the composition ofclaim 1.

11. Leaded gasoline normally in contact with water containing, in amountsufiicient to inhibit corrosion and bromine loss, the composition ofclaim 2.

12. As a new composition of matter, an acetone extract of thecomposition of claim 1.

13. As a new composition of matter, the residue remaining after acetoneextract of the composition of claim 1.

References Cited in the file of this patent UNITED STATES PATENTSSchiller Nov. 27, 1945 Stewart Dec. 17, 1946 OTHER REFERENCES

1. AS A NEW COMPOSITION OF MATER, A PARTIALLY HYDROXYLATED HYDRATE OF AMETALLIC MONOBASIC ACID COMPPOUND PREPARED BY SUBJECTING A HYDRATEDMONOBASIC ACID SALT OF A POLYVALENT METAL SELECTED FROM THE GROUPCONSISTING OF MAGNESIUM, ZINC, THORIUM, CALCIUM, ALUMINUM, LEAD ANDVANADIUM, SAID ACID BEING A MONOBASIC STRAIGHT CHAIN UNSATURATED ACIDCONTAINING FROM ABOUT 10 TO 30 CARBON ATOMS PER MOLECULSE, TO ATEMPERATURE BETWEEN ABOUT 25 AND ABOUT 50* C. FOR A PERIOD SUFFICIENT TOBRING ABOUT A CHANGE IN CHEMICAL COMPOSITION OF SAID SALT, SAID CHANGEBEING AN INCREASE IN THE WEIGHT PERCENT OF SAID METAL IN SAID COMPOUNDOVER THE WEIGHT PERCENT OF SAID METAL IN SAID SALT, SAID INCREASE BEINGINSUFFICIENT TO SATISFY THE WEIGHT PRECENTAGE OF SAID METALTHEORETICALLY REQUIRED BY THE CORRESPONDING BASIC METAL SALT.
 10. LEADEDGASOLINE NORMALLY IN CONTACT WITH WATER CONTAINING, IN AMOUNT SUFFICIENTTO INHIBIT CORROSION AND BROMINE LOSS, THE COMPOSITION OF CLAIM 1.